Alkali metals and their hydrides as catalysts in amine condensation



I Patented Mar. 21, 1950 ALKALI METALS AND THEIR HYDRIDES A S CATALYSTSIN AMINE CONDENSATION Gerald M. Whitman, New Castle, Del, assignor to E.I. du Pont de Ncmonrs & Company, Wilmington, Dei., a corporation ofDelaware No Drawing. Application December 16, 1949, Serial No. 133,483

This invention relates to organic compounds of nitrogen. Moreparticularly, it relates to a. new method for preparing amines.

This application is a continuation-in-part of my copending applicationSerial No. 672,915, filed May 28, 1946, itself a continuation-in-part ofmy application Serial No. 592,271, filed May 5, 1945, and now abandoned.

One of the theoretically simplest and most economical ways of preparingamines consists in adding ammonia or simple amines to the double bond ofolefinic compounds. This reaction proceeds with relative case when theolefinic double bond is activated by a neighboring group, such asanother double bond or a hydroxyl or ester group. Monoolefinichydrocarbons, however, show considerable inertness toward ammonia andamines and consequently require special conditions for addition to thesingle ethylenic bond to take place. It has been proposed heretofore toreact ammonia and amines with monoolefins at elevated temperature andpressure and in the presence of various catalysts such as aminehydrohalides, rare earth phosphates, reduced ammonium molybdate, etc.These prior methods have in general the disadvantage of giving pooryields and of requiring catalysts which are complex and expensive and/orcorrosive to the equipment. Moreover, they are not capable of leading tohigh molecular weight amines, using low molecular weight amines asstarting materials.

This invention has as an object the provision of a new method ofpreparing amines from ammonia-type compounds, i. e., ammonia, primary,secondary, and tertiary amines, and acyclic hydrocarbons that contain acarbon-to-carbon double bond as the sole unsaturation. A further objectis to provide a catalytic method of preparing amines which givessatisfactory yields and uses a cheap non-corrosive catalyst. A stillfurther object is to provide a method of preparing high molecular weightamines from low molecular weight amines. Additional objects will becomeapparent from an examination of the following description and claims.

Theseand other objects and advantages are accomplished according to theherein described invention which comprises reacting under sub-' 15Claima- (Cl. 260-563) 2 taining a carbon-to-carbon double bond as thesole unsaturation, and isolating the amine or stantiallyanhydrousconditions, in the presence amines so formed.

The term ammonia-type compound is used herein and in the appended claimsin its usual and accepted sense to denote ammonia and amines [see, forexample, Karrers Organic Chemistry (English translation, 1938), 20].

One of the reactions involved in the process of this invention is theaddition of a compound of the formula wherein R1 and R2 are hydrogenand/or monovalent organic radicals, or radicals which, togetherwithnitrogen, form a heterocyclic ring, to the double bond of theunsaturated hydrocarbon. With tertiary amines, the reaction mechanism isobscure. It is probable that C-alkylation takes place as well asN-alkylation, and cleavage at the carbon-nitrogen bonds of the originalamine and/or of the amines which form is also a possibility, althoughtertiary amines have heretofore been considered stable in the presenceof alkali metals. The complexity of the reaction is shown by the factthat, if one starts with ammonia or a primary amine, the reactionproduct contains primary, secondary, and tertiary amines; if one startswith a secondary amine, the reaction product contains secondary andtertiary amines; and, if one starts with a tertiary amine, the reactionproduct again contains secondary and tertiary amines. In every case,there is obtained a greater or lesser amount of high boiling. highmolecular weight amines, and usually also a mixture of high boiling,high molecular weight hydrocarbons.

The following examples, in which proportions are in parts by weightunless otherwise specified, are given for illustrative purposes and arenot intended to place any restrictions on the herein describedinvention.

Example I A mixture of h'l3, parts. of. n-butylamine and 8 parts ofmetallicsodiumwasiheated with'agitation in a stainless steel autoclaveunder anethylene pressure of. 800-1000 atmospheres at,,200 C. for tenhours. .During this time a total pressure r 01835 s here el t ide th elction vessel being repressured 'regularlylwith ethylene to maintainthel'press'uife [above 80031111105 pheres. The vessel was cooled, theresidual pres sure released and the contents of the vessel discharged.Filtration of the product recovered 7.8 parts of metallic sodium.Distillation oi the liquid product gave N,N-diethylbutylamine (B. P.135-137 (3.; n 1.4118; neutral equivalent 130.3 compared with thecalculated value of 129.3 for Cal-MN) corresponding to 48% of thetheoretical amount, together with higher-boiling basic materials.

Example [I A mixture of 93 parts of aniline and 8 parts of metallicsodium was heated in an autoclave under 800-1000 atmospheres pressure ofethylene for nine hours at 200 C. During this period the total pressuredrop was 190 atmospheres. Distillation of the filtered product yieldedN-ethylaniline corresponding to 33% of the theoretical amount ofN,N-diethylaniline corresponding to 11% of the theoretical amount,together with some unreacted aniline.

Example III A mixture of 49 parts of anhydrous ammonia, parts of sodiumand 17 parts of n-heptane as a solvent was heated with agitation in apressure vessel under 800-1000 atmospheres pressure of ethylene at 200C. for nine hours. Absorption of ethylene occurred throughout thisperiod, during which a total pressure drop of 930 atmospheres occurred,the vessel being repressured as needed to maintain the pressure above800 atmospheres. The reaction vessel was cooled to 70 C., the residualethylene expanded to atmospheric pressure through condensers at 70 C.and the cold product discharged from the vessel. Distillation of theproduct through a vacuum-jacketed column gave ethylamine, diethylamine,and triethylamine in amounts corresponding to 16%, and 11%,respectively, of the theoretical amounts, together with 29% of theammonia originally charged.

Example IV Example V A mixture of 51 parts of anhydrous ammonia and sixparts of potassium metal was heated in a pressure vessel under 800-1000atmospheres pressure of ethylene at 200 C. for 8.7 hours, during whichtime a total pressure drop of 555 atmospheres was recorded, the vesselbeingrepressured as needed. Fractional distillation of the filteredliquid product gave 15.5 parts of cfzliethylamine and 17.3 parts oftriethylamine.

Example VI w A stainless steel-lined oscillating au lave was flushedwith nitrogen, charged with 5 parts of sodium, cooled in carbondioxide-methanol, and evacuated. Fifty-two (52) parts of anhydrousammonia was added, and the autoclave was pressured with propylene. Thereaction was carried out at 250 C. and 850-975 atmospheres totalpressure. During 18 hours there was a propylene 4 absorptioncorresponding to a pressure drop of 375 atmospheres. Distillation of theproduct gave 41.7 parts of isopropylamine, B. P. 33-34 C., and 7.2 partsof diisopropylamine, B. P. -83 C. The corresponding conversions were 23%and 2.3% respectively, and the total yield, based on the ammoniaconsumed, was of the order of 80%. When the reaction was carried out at480-500 atmospheres pressure, but otherwise under identical conditions,there was obtained 13.2 parts of isopropylamine, corresponding to aconversion of 7.5%.

Example VII The experiment of Example VI was repeated undersubstantially the same conditions but usin as a diluent, 35 parts ofn-heptane. There was obtained 51 parts of isopropylamine, and 7.5 partsof diisopropylamine, representing conversions of 28.9% and 2.5% andyields of 56.8% and 4.9%, respectively.

An identical experiment at 500 atmospheres total pressure gave 24.9parts of isopropylamine and 2.7 parts of diisopropylamine, representingconversions of 14.1% and 0.9% and yields of 30.5% and 1.9%,respectively.

Example VIII A stainless steel-lined oscillating autoclave was flushedwith nitrogen and charged with 5 parts of sodium and 53 parts ofammonia. Isobutylene under hydraulic pressure was admitted into theautoclave and the reaction was run at 250 C. and 855-950 atmospherespressure. During 18 hours there was a pressure drop of 155 atmospheres.Distillation of the product gave 19 parts of tert. butylamine, B. P.43-45 0., corresponding to a conversion of 8.3% and a yield, based onthe ammonia consumed, of 55%.

Example IX In the manner of the preceding examples, a stainlesssteel-lined oscillating autoclave was flushed with nitrogen and chargedwith 7.5 parts of sodium hydride, parts of anhydrous ammonia, and 100parts of ethylene. The vessel was closed and heating and agitation werestarted. During a reaction time of 14% hours at 199-204 C. and 760-960atmospheres ammonia pressure, there was a total pressure drop of 350atmospheres. The autoclave was cooled, opened, and its contentsdischarged. Distillation of the reaction product yielded 86.2 parts ofammonia, 46.6 parts of monoethylamine, 23.3 parts of diethylamine, and10.2 parts of triethylamine. The total conversion, based on the ethylenecharge, was 40.7%. The individual conversions were as follows:ethylamine. 29.0%; diethylamine, 8.9%; triethylamine, 2.8%.

Example X The reaction vessel of Example I)! was charged with 7.5 partsof lithium hydride and 100 parts of anhydrous ammonia and pressured to500 atmospheres with ethylene. During a reaction time of 13% hours at200-202" C., and 850-1000 atmospheres ammonia pressure, there was a dropin pressure of 730 atmospheres. The reaction product consisted of 89.4parts of ammonia, 36.3 parts of monoethylamine, 21.3 parts ofdiethylamine, and 8.4 parts of triethylamine. The total conversion,based on the amount of ammonia originally charged, was 20.1%, and it wasdistributed as follows: monoethylamine, 13.7%; diethyl- 75 amine, 5.0%;triethylamine, 1.4%.

Example XI A mixture of 150 parts of triethylamine and s parts of sodiummetaiwas heated at 250 C. and

under an ethylene pressure of 250 atmospheres in an agitatedcopper-lined autoclave for 16 hours. A total pressure drop of 210atmospheres took place, the vessel being repressured as needed.Fractionation of the product gave 45.7 parts of a liquid boiling abovethe boiling point (89 C.) 01' triethylamine, which liquid consisted of amixture of amines and hydrocarbons.

The products of a number of similar runs (in some of which potassiummetal and sodium hydride were used with equally effective results) werecombined and fractionated to give 870.9 parts of material boiling abovetriethylamine. Extraction of this composite with 6 N hydrochloric acidfollowed by treatment with 40% aqueous potassium hydroxide divided theproduct into 463.3 parts of acid-soluble material and 348.5 parts ofacid-insoluble material.

The acid-soluble portion was fractionated into a number. of cuts boilingbetween 102 C. at atmospheric pressure and 161 C. at 1.5 mm. pressure.Analytical data indicated that this distillate was a mixture of aminescontaining from eight to at least twenty carbon atoms. For example, thei'raction boiling at 134-137 C. at 760 mm. had the composition CaHmN,and infrared spectrographic data indicated that it containedN,N-diethyl-sec. butylamine. It was also uneexpectedly found that theproduct contained secondary, as well as tertiary, amines. For example,the fraction having the composition CmHasN (B. P. 95-97" C. at 0.6 mm.pressure) was found to be a mixture of 46.3% secondary amine and 53.7%tertiary amine.

Fractionation of the acid-insoluble portion gave a number of cutsboiling between 110 C. at atmospheric pressure and 170 C. at 0.125 mm.pressure. dicated that this distillate was a mixture of saturatedaliphatic hydrocarbons, containing a small amount of olefinichydrocarbons.

Example XII A mixture of trimethylamine (150 parts), sodium parts), anddecane (50 parts) reacted with ethylene at 275 C. and 500 atmospheresethylene pressure for 16 hours to'give 11.4 parts of a product boilingabove trimethylamine. This product contained a mixture of high boilingamines.

Example XIV Diethylamine (100 parts) reacted with ethylene in thepresence of sodium metal (10 parts) at 225 C. and 1000 atmospheresethylene pressure for 16 hours to give a product containing 31.1 partsof triethylamine and 138.4 parts of higher boiling material.

From several similar runs the triethylamine was separated bydistillation and the higher boiling products were combined. Thiscomposite Analytical and refractive index data in- 6 in 6 N hydrochloricacid and 238 parts of material insoluble in 6 N hydrochloric acid.

Fractionation oi the acid soluble material gave the following cuts.

Cut N0. Weight Certain analytical data relative to the higher boilingfractions are indicated below:

Amino Distribution Neutraliza- N Cut No. tion 6 m Equivalent PercentPercent Percent P Sewn Tertiary 30a 6 5. 4s Residue 421. 9 4. 57 0 31. 568. 5

These data indicate that the above fractions consisted largely of aminein the range between CnHsiN (N. E.. 213; N% 6.62) and CuHnN (N. E.. 353;N%. 3.97).

The weight distribution of the various amine fractions andacid-insoluble material resulting from the reaction of ethylene anddiethylamine is given below:

PerTCgilt oi Perrggifit oi PgrNCennfi 0 F Reaction Boiling SolubleProduct Product Product olHlhN 17. 4 0. 7 0. 9 1-0 18. 5 22. 3 31. 9 31.9 38. 4 54. 8 20.". 7.2 8.6 7.4 Acid-insoluble portion.. 25. 0 30. 0

The acid-insoluble material was a mixture of very high boilinghydrocarbons with a small amount of nitrogen-containing products.

Example XV A mixture of parts of 3,3,5-trimethylhexylamine and 10 partsof sodium was heated with agitation for 16 hours at 200 C. under 500atmospheres ethylene pressure. Fractionation of the reaction productgave 36.4 parts of N,N-diethyl-3,3,5-trimethylhexylamine (B. P. 104-106"C. at 20 mm. pressure a 1.4311) and 62.9 parts of a higher boilingmaterial which was partly soluble in 6 N hydrochloric acid.

Example XVI A mixture of 78.7 parts of 2-aminopentane and 5 parts ofsodium was heated with agitation for 16 hours at 200 C. under 500atmospheres ethylene pressure. There was obtained 15.4 parts ofN,N-diethy1-2-aminopentane (B. P. 154- 158 C. at 760 mm. pressure) and74.8 parts of a higher boiling product which was partly soluble in 6 Nhydrochloric acid.

Example XVII A mixture of 100 parts of n-butylamine and was separatedinto 549 parts of material soluble 75 10 parts of sodium was heated withagitation for atoms.

1 18 hours at 200 C. under l000;atmospheres ethylene pressure. There wasobtained 68.2 parts of N,N-diethyl-n-buty-lamine and 82.4 parts of aliquid boiling between 41 C. and 205 C. at 1.5 mm. pressure. Thisproduct was 90% soluble in 6 N hydrochloric acid.

Example XVIII n-Amylamine (100 parts) and sodium (10 parts) were reactedwith ethylene as in Example XVII. There was obtained 55.2 parts ofN,N-diethyl-n-amylamine and 73.2 parts of higher boiling amine.

Example XIX Sec.-butylamine (100 parts) and sodium (10 parts) werereacted with ethylene as in Example XVII. There was obtained 31.8 partsof N,N-diethyl-sec.-buty-lamine and 110.9 parts of higher boilingamines.

While this invention has been illustrated with particular reference toethylene, propylene and ,isobutylene, it is to be understood that saidinvention is generic to acyclic hydrocarbons contalning acarbon-to-carbon double bond as the sole unsaturation and having from 2to 6 carbon Terminally unsaturated acyclic monooleflnic hydrocarbons, i.e., those in which the double bond is between the carbon atoms in the1,2 positions react most readily and are, therefore, preferred in myprocess. Other examples of suitable unsaturated hydrocarbons arepentene-l. butene-l, hexene-i and the like. or these, ethylene is by farthe most useful.

While this invention has been illustrated with a particular reference toammonia and certain specific amines, it is to be understood that saidinvention is generic to all basic ammonia-type compounds of the groupconsisting of ammonia, amines having hydrogen attached to aminonitrogen, that is primary and secondary amines and amines having nohydrogen attached to amino nitrogen, that is tertiary amines. Includedamong examples of said basic ammonia-type compounds in addition to thosealready listed are: methylamine, ethylamine, dimethylamine, octylamine,cyclohexylamine, dicyclohexylamine.

'dodecylamine, ocetadecylamine, pyrrolidine, piperidine.

benzylamine, hexamethylenediamine. tripropylarnine, tri-n-hexylamine,and the like. Mixtures of two or more monoolefins and/or two or moreammonia-type compounds may be used. However, I prefer to employ ammoniaand primary or'secondary hydrocarbon amines, particularly alhlamines,since-they give a higher ratio of amines to hydrocarbons than dotertiary amines. Further, I prefer to employ amines free of aliphaticunsaturation. Unsaturated amines such as allylamine and methallylaminedo react with unsaturated hydrocarbons such as ethylene in the presenceof alkali metals, but in such cases the reaction is complicated byself-condensation of the unsaturated amines and it is less clear-cut. Ifthe process is to be used in the preparation of high molecular weightamines, it is cheaper to start with primary or secondary alkylamines ofone to eighteen carbon atoms of which those having not more than eightcarbon atoms are especially preferred. However, tertiary amines of up toeighteen or more carbon atoms can be used. of which hydrocarbon tertiaryamines free from aliphatic unsaturation, such as tertiary alkylamines.are preferable.

tary alkali metals. Included among examples of members of this groupare: elementary potassium, elementary lithium, sodium hydride, lithiumhydride, and potassium hydride. Elementary sodium is preferred onaccount of the fact that it is the cheapest and most readily availablemember of this group.

The reactants can be used in any desired relative proportions. It isoften advantageous to use an excess or the cheaper reactant (e. g.,ammonia or ethylene) to force the reaction nearer completion. The amountof catalyst is not particularly critical. It is in general used inproportions of 003-04 gram atom (calculated on the basis or the alkalimetal content thereof) per mol of ammonia-type compound, although aslittle as 0.01 or as much as one or even five gram atoms per mol may beused. Obviously, the smallest quantity consistent with efficientoperation should be used.

An inert solvent or diluent may be used if desired, preferably an inerthydrocarbon, i. e., a hydrocarbon free from non-benzenoid unsaturation(1. e., a hydrocarbon of the group consisting of aromatic and saturatedacyclic and alicyclic hydrocarbons), such as kerosene, cyclohexane,benzene, and the like.

A critical factor in the process of this invention isthe pressure.Experience has shown that a pressure of at least 225 atmospheres isessential if practical yields are to be obtained. Preferably, on accountof the superior yields had therewith. the pressure should exceed 500atmospheres and it can be as high as the equipment will withstand.Optimum results are had at pressures not lower than 800 atmospheres, adesirable pressure range being 800-1200 atmospheres In general theautogenous pressure developed by the reactants at reaction temperatureis insuiiicient. and it is. therefore. necessary to apply extraneouspressure. This can be done by compression of a reactive gas likeethylene or propylene when this as is itself the reactant. Liquidreactants can be compressed hydrostatically, for example, by placingthem in a flexible metal container which is subjected to oil pressure.Alternatively, the liquid reactant can be compressed directly by anappropriate non-miscible fluid which is in turn compressed by a pump,the reactant being forced through a purification chamber into thereactor. The reactant compressed in this manner can be either theunsaturated hydrocarbon or the ammonia-type compound.

The reaction temperature is also a critical factor. A temperature of atleast C. is essential to the obtainment of practical yields. Thereaction is impracticably slow below 100' C., even at high pressures.Preferably, in order to obtain maximum yields. the temperature should behigher than C. It can be as high as the reactants will stand withoutdecomposition, the preferred range being C.-300 C since optimum resultsare had at temperatures within said range.

The reaction time depends upon the choice of reactants, the temperature,and the pressure. In general, at a temperature of C.-200 C. and apressure of 800-1000 atmospheres, satisfactory yields are obtainedwithin 5-10 hours As could be expected, not all unsaturated hydrocarbonsreact at the same rate in the process 01' this invention. Ethylene ismost effective; it reacts with ammonia and amines 1n appreciable amountsat the lowest range of pressure and temperature disclosed. The higherolefins, e. g., propylene and isobutylene may, and

accuse in general do, require more drastic conditions, particularlyhigher pressures. The same is true of amines, as some of them are morereactive than others. It is, however, a matter of simple experimentationto determine with any given unsaturated hydrocarbon or amine theconditions which favor a. relatively high rate of reaction. In thisconnection, it may be pointed out that a set ofconditions which giveswhat appears to be a relatively low conversion to amines may be entirelypractical and even sometimes desirable, since it is feasible inindustrial practice to recycle the unused reactants over the catalystand thus achieve high conversions in several passes.

My new method for preparing amines possesses advantages not previouslycombined in any single process. For example, my novel process readilyprovides amines in excellent yields. Furthermore, the catalyst employedin said process is readily obtained, is relatively inexpensive and issubstantially inert toward the equipment in H which the said process iseffected.

A particular and entirely unexpected advantage of the process is that itmakes possible the production of high molecular weight amines fromsimple, low molecular weight amines such as diethylamine and cheapunsaturates such as ethylene. As has been shown, mixtures of' amineshaving up to 24 carbon atoms and even more can thus be obtainedconveniently and economically. High molecular weight amines, e. g.,those in the 10 to 20earbon atom range, find uses in such varied fieldsas rodent repellents, corrosion inhibitors, flotation agents for ironore, textile chemical intermediates, surface-active agents,

etc.

As many apparently widely difierent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

I claim:

1. In a process for obtaining an amine, the step of heating a basicammonia-type compound of the group consisting of ammonia and amines withan acyclic hydrocarbon containing not more than six carbon atoms and, asthe sole unsaturation, a double bond between the carbon atoms in the1,2-positions, said heating being effected under substantially anhydrousconditions at a temperature of at least 100 C. under a pressure of atleast 225 atmospheres in the presence, as catalyst, of a member of thegroup consisting of alkali metal hydrides and elementary alkali metals.

2. In a process for obtaining an amine as set forth in claim 1, saidheating being eiIected as therein set forth and in the presence of ahydrocarbon free from non-benzenoid unsaturation as solvent.

3. In a process for obtaining an amine, the step of heating ammonia withan acyclic hydrocarbon containing not more than six carbon atoms and, asthe sole unsaturation, a double bond between the carbon atoms in the1,2-positions, said heating being effected under substantially anhydrousconditions at'a temperature of at least 100 C. under a pressure of atleast 225 atmospheres in the presence, as catalyst, of a member of theof heating an amine having hydrogen attached to amino nitrogen with anacyclic hydrocarbon containing not more than six carbon atoms and,

as'the-sole'usaturation. a double bond between the carbon atoms in the1,2-positions', said heating being effected under substantiallyanhydrous conditions at a temperature of at least C. under a pressure ofat least'225 atmospheres in the presence, as catalyst, of a member ofthe group consisting of alkali metal hydrides and elementary alkalimetals. 1

-5. In a process for-obtaining an amine, the step of heating a tertiaryamine with an acyclic hydrocarbon containing not more than six carbonatoms and, as the sole unsaturation, a double bond between the carbonatoms in the 1,2-positions, said heating being eflected undersubstantially anhydrous conditions at a temperature of at least 100 C.under a pressure of at least 225 atmospheres'in the presence, ascatalyst, of a member of the group consisting of alkalimetal hydridesand elementary alkali metals.

6. In a process for obtaining an amine, the step of heating a basicammonia-type compound of the group consisting oi ammonia and amines withan acyclic hydrocarbon containing not more than six carbon atoms and, asthe sole unsaturation, a double bond between the carbon atoms in the1,2-positions, said heating being effected under substantially anhydrousconditions at a temperature of at least C. under a pressure of at least500 atmospheres in the presence, as catalyst, of a member of the groupconsisting of alkali metal hydrides and elementary alkali metals.

'7. In a process for obtaining an amine as set forth in claim 6, saidheating being effected as therein set forth and in the presence of ahydrocarbon free from non-benzenoid unstaturation a solvent. r

8. In a process for obtaining an amine, the step of heating analkylamine having hydrogen attached to amino nitrogen with an acyclichydrocarbon containing not more than six carbon atoms and, as the soleunsaturation, a double bond between the carbon atoms in the1,2-positions, said heating being eflected under substantially anhydrousconditions at a temperature of at least 150 C. under a pressure .of atleast 500 I atmospheres in the presence, as catalyst, of a member of thegroup consisting 'of alkali metal hydrides and elementary alkali metals.I

9. In a process for obtaining an amine, the step of heating a tertiaryalkylamine with an acyclic hydrocarbon containing not more than sixcarbon atoms and, as the sole unsaturation a double bond between thecarbon atoms in the 1,2-positions, said heating being eflected undersubstantially anhydrous conditions at a temperature of at least 150 C.under a pressure of at least 500 atmospheres in the presence, ascatalyst, of a member of the group consisting of alkali metal hydridesand elementary alkali metals.

10. In a, process for obtaining an amine, the step of heating a basicammonia-type compound of the group consisting of ammonia and amines withethylene, said heating being eflected under substantially anhydrousconditions at a temperature within the range of from to 300 C. undera-pressure of at least 800 atmospheres in the presence, as catalyst, ofa member of the group consisting of alkali metal hydrides and elementaryalkali metals.

11. A process for obtaining an amine as set forth in claim 10 whereinsaid catalyst is an al- I kali metal hydride.

12. A process for obtaining an amine as set 13. Inaprooesstorobtaininganamineasset forth in claim 10, said heating being efl'ected astherein set forth and in the presence of a hydrocarbon free fromnon-benzenoid unsaturation as solvent.

1'4. In a process for obtaining an amine, the step of heatinz ammonia.with ethylene, said heatin: being eitected under substantially anhydrousconditions at a temperature within the reuse 0! 12 from 175 C. to 800 C.under a pressure within the range of from 800 to 1200 atmospheres in thepresence of elementary sodium as catalyst.

15. In a process for obtaining an amine as set forth in claim 14, saidheating being eflected as therein set forth and in the presence oi. ahydrocarbon free from non-benzenoid unsaturation as solvent.

GERALD M. WHITMAN.

No references cited.

1. IN A PROCESS FOR OBTAINING AN AMINE, THE STEP OF HEATING A BASICAMMONIA-TYPE COMPOUND OF THE GROUP CONSISTING OF AMMONIA AND AMINES WITHAN ACYCLIC HYDROCARBON CONTAINING NOT MORE THAN SIX CARBON ATOMS AND, ASTHE SOLE UNSATURATION, A DOUBLE BOND BETWEEN THE CARBON ATOMS IN THE1,2-POSITIONS, SAID HEATING BEING EFFECTED UNDER SUBSTANTIALLY ANHYDROUSCONDITIONS AT A TEMPERATURE OF AT LEAST 100*C. UNDER A PRESSURE OF ATLEAST 225 ATMOSPHERES IN THE PRESENCE, AS CATALYST OF A MEMBER OF THEGROUP CONSISTING OF ALKALI METAL HYDRIDES AND ELEMENTARY ALKALI METALS.